Ligand-Dependent Colloidal Stability Controls the Growth of Aluminum Nanocrystals

• Published in: Journal of the American Chemical Society Vol. 141; no. 4; pp. 1716 - 1724
• Main Authors: Clark, Benjamin D, DeSantis, Christopher J, Wu, Gang, Renard, David, McClain, Michael J, Bursi, Luca, Tsai, Ah-Lim, Nordlander, Peter, Halas, Naomi J
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 30.01.2019
• Subjects: Aluminum - chemistry; Colloids; Ligands; Metal Nanoparticles - chemistry; Models, Molecular; Molecular Conformation; Solvents - chemistry
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.8b12255

The precise size- and shape-controlled synthesis of monodisperse Al nanocrystals remains an open challenge, limiting their utility for numerous applications that would take advantage of their size and shape-dependent optical properties. Here we pursue a molecular-level understanding of the formation of Al nanocrystals by titanium­(IV) isopropoxide-catalyzed decomposition of AlH3 in Lewis base solvents. As determined by electron paramagnetic resonance spectroscopy of intermediates, the reaction begins with the formation of Ti3+-AlH3 complexes. Proton nuclear magnetic resonance spectroscopy indicates isopropoxy ligands are removed from Ti by Al, producing aluminum­(III) isopropoxide and low-valent Ti3+ catalysts. These Ti3+ species catalyze elimination of H2 from AlH3 inducing the polymerization of AlH3 into colloidally unstable low-valent aluminum hydride clusters. These clusters coalesce and grow while expelling H2 to form colloidally stable Al nanocrystals. The colloidal stability of the Al nanocrystals and their size is determined by the molecular structure and density of coordinating atoms in the reaction, which is controlled by choice of solvent composition.